CN106582501A - Desulfuration adsorbent - Google Patents
Desulfuration adsorbent Download PDFInfo
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- CN106582501A CN106582501A CN201611235471.6A CN201611235471A CN106582501A CN 106582501 A CN106582501 A CN 106582501A CN 201611235471 A CN201611235471 A CN 201611235471A CN 106582501 A CN106582501 A CN 106582501A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0214—Compounds of V, Nb, Ta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a desulfuration adsorbent. The desulfuration adsorbent is composed of the following raw materials of, by weight, 33-41 parts of nano attapulgite, 1-5 parts of cyclohexyl methyl ketone, 7-15 parts of acrylic acid, and 11-19 parts of ammonium metavanadate. According to the desulfuration adsorbent, the nano attapulgite serves as one of the raw materials and mixed with the cyclohexyl methyl ketone, grinding is conducted, and the ammonium metavanadate, the acrylic acid and the like are used for treatment, so that the desulfuration adsorbent is prepared; the desulfuration adsorbent prepared in the this way is large in sulfur capacity, good in sulfur selectivity, high in desulfuration percent and capable of reducing sulfur to 1ppmw; and in addition, the desulfuration adsorbent is long in service life, environmentally friendly and free of secondary pollution. The preparation process of the desulfuration adsorbent is simple, operation and control are easy, the performance is stable, the production cost is low, and the desulfuration adsorbent is suitable for industrialized production. When the desulfuration adsorbent is used for desulfuration of gasoline, the process operating conditions are mild, dsulfuration can be conducted under ordinary pressure and at a low temperature, accordingly energy consumption is reduced, and the operation cost is lowered.
Description
Technical field
The present invention relates to sulfur removal material technical field, specifically a kind of desulfuration adsorbent.
Background technology
The ultra-deep desulfurization of gasoline has become a major issue urgently to be resolved hurrily in world wide.Combustion of sulfur in gasoline
It is one of pollutant main in air to generate oxysulfide (SOx), and it is discharged in air can form acid rain, the ecological ring of destruction
Border.In addition, sulfur oxide can also corrosion and damage engine components, make motor-driven vehicle gas disposal catalyst poisoning, reduce it and urge
Change activity, increase the discharge of particulate pollutant, increase the pollution of urban environment.Therefore, it is motor petrol standard to limit sulfur content
In an important indicator, be also evaluate gasoline cleaning degree key factor.External gasoline blend component only has 34% in constituting
It is catalytic cracking (FCC) gasoline, the blend component of the product oil of China has 80% (volume fraction) from FCC gasoline, and gasoline
The sulphur source of middle 85-95% from FCC gasoline, therefore, the sulfur content being effectively reduced using which kind of technique in FCC gasoline becomes China
The matter of utmost importance that quality of gasoline upgrading faces.
Traditional gasoline desulfurization technology can be divided into hydrodesulfurization and two kinds of desulfurization of absorption.Hydrodesulfurization need high temperature, high pressure,
Substantial amounts of hydrogen wastage, also can cause the significantly loss of octane number with the saturation of olefin(e) compound.Absorption method gasoline desulfurization
There is Low investment, lower operational cost.But it is not enough below desulfurizing agent generally existing of the prior art：1st, desulfurization depth
Not enough, it is difficult to sulphur is taken off to below 5ppmw；2nd, adsorbent specific surface area is relatively low, and absorption Sulfur capacity is relatively limited；3rd, sweetening process
Operating condition is harsh and energy consumption is big, and operating cost is higher；4th, sweetening process is unfriendly to environment；5th, the selectivity of desulfurizing agent
Low, the life-span is shorter.It is few using nanometer concavo-convex rod soil additionally, the material such as the more employing activated carbon of existing desulfurizing agent, ZSM-5
Relevant information.
The content of the invention
It is an object of the invention to provide a kind of desulfuration adsorbent, to solve the problems, such as above-mentioned background technology in propose.
For achieving the above object, the present invention provides following technical scheme：
A kind of desulfuration adsorbent, is made up of the following raw material according to weight portion：Nanometer concavo-convex rod soil 33-41 part, MIBK
Cyclohexyl 1-5 parts, acrylic acid 7-15 parts, ammonium metavanadate 11-19 parts.
As further scheme of the invention：The desulfuration adsorbent, is made up of the following raw material according to weight portion：Nanometer
Concavo-convex rod soil 35-39 part, MIBK cyclohexyl 2-4 parts, acrylic acid 9-13 parts, ammonium metavanadate 13-17 parts.
As further scheme of the invention：The desulfuration adsorbent, is made up of the following raw material according to weight portion：Nanometer
37 parts of concavo-convex rod soil, 3 parts of MIBK cyclohexyl, 11 parts of acrylic acid, 15 parts of ammonium metavanadate.
Another object of the present invention is to provide a kind of preparation method of desulfuration adsorbent, comprises the steps of：
1) deionized water of 6.1 times of ammonium metavanadate and its quality is mixed, ammonium metavanadate solution is obtained；By acrylic acid and its
The absolute ethyl alcohol mixing that 2.7 times of quality, is obtained acrylic acid solution；
2) by nanometer concavo-convex rod soil and MIBK cyclohexyl mixed grinding, 120 mesh sieves excessively, it is subsequently adding ammonium metavanadate molten
Liquid, is warming up to 72 DEG C and seals stir process 2.1h at such a temperature, is subsequently adding acrylic acid solution, is warming up to 89 DEG C and at this
At a temperature of heating stirring process 15min, then ultrasonically treated 33min at such a temperature, ultrasonic power is 900W, then in 99-101
Stir at a temperature of DEG C to dry, then 4.3h is calcined in 450 DEG C of Muffle furnace and obtain final product desulfuration adsorbent.
Another object of the present invention is to provide desulfuration adsorbent application in the oil.
Compared with prior art, the invention has the beneficial effects as follows：
The present invention with nanometer concavo-convex rod soil as raw material, after MIBK cyclohexyl mixed grinding, then through ammonium metavanadate, third
Desulfuration adsorbent obtained in process of olefin(e) acid etc., Sulfur capacity is big, desulfurization depth good to the selectivity of sulphur is high, can by sulphur take off to
1ppmw；In addition long service life, more friendly to environment, non-secondary pollution, renewable recycling.The desulfurization of the present invention is inhaled
Attached dose when desulfurization is carried out to gasoline process condition it is gentle, can carry out under normal pressure and lower temperature, saving energy consumption, reduce
Running cost.Preparation process is simple of the present invention, easy to operate, easy to control, stable performance, low production cost is suitable to industrialized production.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of desulfuration adsorbent is made up of the following raw material according to weight portion：Nanometer concavo-convex rod soil
33 parts, 1 part of MIBK cyclohexyl, 7 parts of acrylic acid, 11 parts of ammonium metavanadate.
6.1 times of deionized water of ammonium metavanadate and its quality is mixed, ammonium metavanadate solution is obtained；By acrylic acid and its matter
The absolute ethyl alcohol mixing of 2.7 times of amount, is obtained acrylic acid solution.By nanometer concavo-convex rod soil and MIBK cyclohexyl mixed grinding, mistake
120 mesh sieves, are subsequently adding ammonium metavanadate solution, are warming up to 72 DEG C and seal stir process 2.1h at such a temperature, are subsequently adding
Acrylic acid solution, is warming up to 89 DEG C and at such a temperature heating stirring processes 15min, then ultrasonically treated at such a temperature
33min, ultrasonic power is 900W, then is stirred at a temperature of 99 DEG C to doing, and then 4.3h is calcined in 450 DEG C of Muffle furnace is
Obtain desulfuration adsorbent.
Embodiment 2
In the embodiment of the present invention, a kind of desulfuration adsorbent is made up of the following raw material according to weight portion：Nanometer concavo-convex rod soil
41 parts, 5 parts of MIBK cyclohexyl, 15 parts of acrylic acid, 19 parts of ammonium metavanadate.
6.1 times of deionized water of ammonium metavanadate and its quality is mixed, ammonium metavanadate solution is obtained；By acrylic acid and its matter
The absolute ethyl alcohol mixing of 2.7 times of amount, is obtained acrylic acid solution.By nanometer concavo-convex rod soil and MIBK cyclohexyl mixed grinding, mistake
120 mesh sieves, are subsequently adding ammonium metavanadate solution, are warming up to 72 DEG C and seal stir process 2.1h at such a temperature, are subsequently adding
Acrylic acid solution, is warming up to 89 DEG C and at such a temperature heating stirring processes 15min, then ultrasonically treated at such a temperature
33min, ultrasonic power is 900W, then is stirred at a temperature of 101 DEG C to dry, then calcines 4.3h in 450 DEG C of Muffle furnace
Obtain final product desulfuration adsorbent.
Embodiment 3
In the embodiment of the present invention, a kind of desulfuration adsorbent is made up of the following raw material according to weight portion：Nanometer concavo-convex rod soil
35 parts, 2 parts of MIBK cyclohexyl, 9 parts of acrylic acid, 13 parts of ammonium metavanadate.
6.1 times of deionized water of ammonium metavanadate and its quality is mixed, ammonium metavanadate solution is obtained；By acrylic acid and its matter
The absolute ethyl alcohol mixing of 2.7 times of amount, is obtained acrylic acid solution.By nanometer concavo-convex rod soil and MIBK cyclohexyl mixed grinding, mistake
120 mesh sieves, are subsequently adding ammonium metavanadate solution, are warming up to 72 DEG C and seal stir process 2.1h at such a temperature, are subsequently adding
Acrylic acid solution, is warming up to 89 DEG C and at such a temperature heating stirring processes 15min, then ultrasonically treated at such a temperature
33min, ultrasonic power is 900W, then is stirred at a temperature of 100 DEG C to dry, then calcines 4.3h in 450 DEG C of Muffle furnace
Obtain final product desulfuration adsorbent.
Embodiment 4
In the embodiment of the present invention, a kind of desulfuration adsorbent is made up of the following raw material according to weight portion：Nanometer concavo-convex rod soil
39 parts, 4 parts of MIBK cyclohexyl, 13 parts of acrylic acid, 17 parts of ammonium metavanadate.
6.1 times of deionized water of ammonium metavanadate and its quality is mixed, ammonium metavanadate solution is obtained；By acrylic acid and its matter
The absolute ethyl alcohol mixing of 2.7 times of amount, is obtained acrylic acid solution.By nanometer concavo-convex rod soil and MIBK cyclohexyl mixed grinding, mistake
120 mesh sieves, are subsequently adding ammonium metavanadate solution, are warming up to 72 DEG C and seal stir process 2.1h at such a temperature, are subsequently adding
Acrylic acid solution, is warming up to 89 DEG C and at such a temperature heating stirring processes 15min, then ultrasonically treated at such a temperature
33min, ultrasonic power is 900W, then is stirred at a temperature of 100 DEG C to dry, then calcines 4.3h in 450 DEG C of Muffle furnace
Obtain final product desulfuration adsorbent.
Embodiment 5
In the embodiment of the present invention, a kind of desulfuration adsorbent is made up of the following raw material according to weight portion：Nanometer concavo-convex rod soil
37 parts, 3 parts of MIBK cyclohexyl, 11 parts of acrylic acid, 15 parts of ammonium metavanadate.
6.1 times of deionized water of ammonium metavanadate and its quality is mixed, ammonium metavanadate solution is obtained；By acrylic acid and its matter
The absolute ethyl alcohol mixing of 2.7 times of amount, is obtained acrylic acid solution.By nanometer concavo-convex rod soil and MIBK cyclohexyl mixed grinding, mistake
120 mesh sieves, are subsequently adding ammonium metavanadate solution, are warming up to 72 DEG C and seal stir process 2.1h at such a temperature, are subsequently adding
Acrylic acid solution, is warming up to 89 DEG C and at such a temperature heating stirring processes 15min, then ultrasonically treated at such a temperature
33min, ultrasonic power is 900W, then is stirred at a temperature of 100 DEG C to dry, then calcines 4.3h in 450 DEG C of Muffle furnace
Obtain final product desulfuration adsorbent.
Comparative example 1
In addition to MIBK cyclohexyl is not contained, its material content and preparation process are consistent with embodiment 5.
Comparative example 2
In addition to acrylic acid is not contained, its material content and preparation process are consistent with embodiment 5.
Comparative example 3
In addition to MIBK cyclohexyl and acrylic acid is not contained, its material content and preparation process are consistent with embodiment 5.
Embodiment 6
The specific surface area of detection embodiment of the present invention 1-5 and adsorbent obtained in comparative example 1-3, as shown in table 1.While with
The nanometer concavo-convex rod soil for not making any process is blank.
Table 1
| Total specific surface area SBET/ (m2·g-1) | |
| Embodiment 1 | 190.4 |
| Embodiment 2 | 191.7 |
| Embodiment 3 | 238.7 |
| Embodiment 4 | 250.5 |
| Embodiment 5 | 269.2 |
| Comparative example 1 | 33.7 |
| Comparative example 2 | 93.4 |
| Comparative example 3 | 25.1 |
| Untreated nanometer concavo-convex rod soil | 7.3 |
Embodiment 7
Desulfuration adsorbent prepared by above-described embodiment 5 and comparative example 1-3 is filled in fixed bed reactors respectively, to help
Southern catalytically cracked gasoline is raw material (its composition is shown in Table 2), in the case where temperature is 30 DEG C and condition of normal pressure, with the stream of 0.5mL/min
Speed implements respectively the absorption desulfurization test of continuous 10 hours, and absorption Desulfurization Test Results are shown in Table 3, and wherein Sulfur capacity is 1g desulfurization absorption
The total sulfur content (in gram) that agent is removed when the total sulfur content in gasoline stocks is down to into below 10ppmw, for example Sulfur capacity is
When 0.525, the total sulfur content removed when the total sulfur content in gasoline stocks is down to below 10ppmw by 1g desulfuration adsorbents is represented
For 0.525g.
The composition of the feed gasoline of table 2
The absorption Desulfurization Test Results of the desulfuration adsorbent of table 3
As seen from the results in Table 3：
1st, desulfuration adsorbent desulfurization depth prepared by the present invention is high, can be by feed gasoline in absorption desulfurization 5-6 hours
Sulphur be down to below 1ppmw, and service life is up to 10h or so；Additionally, its desulfuration adsorbent Sulfur capacity is big, particularly to thiophene
Fen and its selectivity of derivative are good.
When the 2nd, not containing acrylic acid, the service life of desulfuration adsorbent is greatly shortened；When not containing MIBK cyclohexyl, take off
Selectivity of the sulfur absorbent to sulphur is low；And when not containing MIBK cyclohexyl and acrylic acid, the Sulfur capacity of desulfuration adsorbent is less,
And service life is short.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of spirit or essential attributes without departing substantially from the present invention, the present invention can be in other specific forms realized.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit is required rather than described above is limited, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity those skilled in the art should
Using specification as an entirety, the technical scheme in each embodiment can also Jing it is appropriately combined, form those skilled in the art
Understandable other embodiment.
Claims (5)
1. a kind of desulfuration adsorbent, it is characterised in that be made up of the following raw material according to weight portion：Nanometer concavo-convex rod soil 33-41
Part, MIBK cyclohexyl 1-5 parts, acrylic acid 7-15 parts, ammonium metavanadate 11-19 parts.
2. desulfuration adsorbent according to claim 1, it is characterised in that be made up of the following raw material according to weight portion：Receive
Rice concavo-convex rod soil 35-39 part, MIBK cyclohexyl 2-4 parts, acrylic acid 9-13 parts, ammonium metavanadate 13-17 parts.
3. desulfuration adsorbent according to claim 1, it is characterised in that be made up of the following raw material according to weight portion：Receive
37 parts of concavo-convex rod soil of rice, 3 parts of MIBK cyclohexyl, 11 parts of acrylic acid, 15 parts of ammonium metavanadate.
4. a kind of preparation method of the desulfuration adsorbent as described in claim 1-3 is arbitrary, it is characterised in that by following steps group
Into：
1) deionized water of 6.1 times of ammonium metavanadate and its quality is mixed, ammonium metavanadate solution is obtained；By acrylic acid and its quality
2.7 times of absolute ethyl alcohol mixing, is obtained acrylic acid solution；
2) by nanometer concavo-convex rod soil and MIBK cyclohexyl mixed grinding, 120 mesh sieves excessively, ammonium metavanadate solution is subsequently adding, is risen
Temperature is to 72 DEG C and seals stir process 2.1h at such a temperature, is subsequently adding acrylic acid solution, is warming up to 89 DEG C and in the temperature
Lower heating stirring processes 15min, then ultrasonically treated 33min at such a temperature, and ultrasonic power is 900W, then at 99-101 DEG C
At a temperature of stir to dry, then 4.3h is calcined in 450 DEG C of Muffle furnace and obtains final product desulfuration adsorbent.
5. the application in the oil of the desulfuration adsorbent as described in claim 1-3 is arbitrary.
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|---|---|---|---|
| CN201611235471.6A CN106582501A (en) | 2016-12-28 | 2016-12-28 | Desulfuration adsorbent |
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| CN201611235471.6A CN106582501A (en) | 2016-12-28 | 2016-12-28 | Desulfuration adsorbent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181398A (en) * | 2018-09-17 | 2019-01-11 | 明光市飞洲新材料有限公司 | A kind of building coating resist sagging adsorbent and preparation method thereof |
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2016
- 2016-12-28 CN CN201611235471.6A patent/CN106582501A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181398A (en) * | 2018-09-17 | 2019-01-11 | 明光市飞洲新材料有限公司 | A kind of building coating resist sagging adsorbent and preparation method thereof |
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